Relative photoionization cross sections for O + and O 2+ produced by the Auger decay of a 1s hole in atomic oxygen were measured by using synchrotron radiation between 525 and 553 eV. Energies and quantum defects of the members of the two Rydberg series converging to [1s]2s 2 2p 4 ( 4 P) and [1s]2s 2 2p 4 ( 2 P) ionization thresholds were determined. In addition, the 2 P and 4 P ionization thresholds were calculated from the two Rydberg series. The 182 meV resolution of the monochromator allowed a detailed study over both thresholds revealing evidence for post-collision interaction and allowing a comparison of the ionization continuum above both 2 P and 4 P thresholds with that of the ionization continuum above the Ar L 2-3 edges. This comparison indicates that the lifetimes of the Ar(2p) and O(1s) hole states are approximately the same.

The independent particle approximation is shown to break down for the photoionization of both inner and outer nᐉ ͑ᐉ . 0͒ electrons of all atoms, at high enough energy, owing to interchannel interactions with the nearby ns photoionization channels. The effect is illustrated for Ne 2p in the 1 keV photon energy range through a comparison of theory and experiment. The implications for x-ray photoelectron spectroscopy of molecules and condensed matter are discussed. [S0031-9007 (97)03382-6] PACS numbers: 32.80.Fb

Anion-yield spectroscopy using x rays is shown to be a selective probe of molecular core-level processes, providing unique experimental verification of shape resonances. For CO, partial anion and cation yields are presented for photon energies near the C K edge. The O- yield exhibits features above threshold related only to doubly excited states, in contrast to cation yields which also exhibit pronounced structure due to the well-known sigma* shape resonance. Because the shape resonance is completely suppressed for O-, anion spectroscopy thus constitutes a highly selective probe, yielding information unobtainable with absorption or electron spectroscopy.

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